EP2305719B1 - Verfahren zur herstellung eines olefinpolymerisierungskatalysators und olefinpolymerisierungsverfahren damit - Google Patents

Verfahren zur herstellung eines olefinpolymerisierungskatalysators und olefinpolymerisierungsverfahren damit Download PDF

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EP2305719B1
EP2305719B1 EP09800508.5A EP09800508A EP2305719B1 EP 2305719 B1 EP2305719 B1 EP 2305719B1 EP 09800508 A EP09800508 A EP 09800508A EP 2305719 B1 EP2305719 B1 EP 2305719B1
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group
carbon atoms
formula
catalyst
olefin polymerization
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EP2305719A2 (de
EP2305719A4 (de
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Sah-Mun Hong
Sung-Woo Kang
Young-Jae Jun
Byung-Keel Sohn
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DL Holdings Co Ltd
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Daelim Industrial Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • This invention relates to a method for preparing an olefin polymerization catalyst and an olefin polymerization method using the same. More particularly, this invention relates to an olefin polymerization catalyst which can be produced by a simple process, has a desirable polymerization activity, can produce a polyolefin of a low melt index and a high molecular weight, and can control a molecular weight distribution and a composition of the produced olefin polymer or copolymer.
  • an olefin polymer having desirable physical properties can be obtained.
  • a metallocene catalyst system consisting of an organometallic compound(generally, metallocene) and an activator such as aluminoxane has been used as shown in German Patent No. 3,007,725 , U.S. Patent Nos. 4,404,344 , 4,874,880 and 5,324,800 .
  • the organometallic compound has ligands such as a cyclopentadienyl group, an indenyl group, a cycloheptadienyl group and a fluorenyl group to control a stereoregularity and a molecular weight of the produced polymer.
  • ligands such as a cyclopentadienyl group, an indenyl group, a cycloheptadienyl group and a fluorenyl group to control a stereoregularity and a molecular weight of the produced polymer.
  • the metallocene compound and the activator are supported by an inorganic carrier to produce a non-uniform solid catalyst, and the non-uniform solid catalyst is used for a slurry or a gas phase polymerization process to control the particle shape of the produced polymer as shown in U.S. Patent No. 4,808,561 and Korean Patent application No. 1998-44308 .
  • the conventional metallocene catalyst system requires a metallocene compound as a catalyst which is obtained by several reaction steps under complicated reaction conditions. Therefore, the conventional metallocene catalyst system increases the production cost of a polyolefin, and a polyolefin of a high molecular weight cannot be easily produced.
  • an object of the present invention to provide an olefin polymerization catalyst which can be produced by a simple process and can have various catalytic properties in accordance with the combination of its components.
  • the olefin polymerization catalyst has a desirable polymerization activity, and can produce a tailor-made polymer having a relatively high molecular weight, and thus commercially desirable.
  • the present invention provides a method for preparing an olefin polymerization catalyst comprising: first mixing an organic compound of Formula 1; an organometallic compound of Formula 2 and an aluminoxane, and then adding thereto a reaction mixture of an organic transition metal compound of Formula 3 and mixing, wherein: [Formula 1] R 1 -H or R 1 -Q-R 1 in Formula 1, R 1 is a cyclic hydrocarbyl group of 5 to 30 carbon atoms having at least 2 conjugated double bonds, and Q is a divalent group for bridging R 1 s selected from the group consisting of (CR 5 2 ) b , (SiR 5 2 ) b , (GeR 5 2 ) b , NR 5 and PR 5 , wherein the substituent R 5 is independently a hydrogen atom, an alkyl radical of 1 to 20 carbon atoms, a cycloalkyl radical of 3 to 20 carbon atoms, an alkenyl radical of 1
  • the present invention also provides an olefin polymerization catalyst in which the catalyst including the organic compound of Formula 1, the organometallic compound of Formula 2, the organic transition metal compound of Formula 3, and the aluminoxane is contacted with an organic or inorganic carrier.
  • the present invention also provides an olefin polymerization method including the step of polymerizing at least one olefin in the presence of the polymerization catalyst.
  • the method for preparing an olefin polymerization catalyst according to the present invention may have various combinations by selecting the organic compound, the organometallic compound, and the organic transition metal compound, and can be used to prepare various polymers having a relatively high molecular weight according to the user's need.
  • the catalyst can be produced by a simple process which minimizes the manufacturing time and manufacturing steps for producing the catalyst.
  • the olefin polymerization catalyst has a desirable polymerization activity, which increases the productivity of polyolefin.
  • the molecular weight, the molecular weight distribution, and the composition of the produced olefin polymer or copolymer can be easily controlled in an uniform phase(solution) or a non-uniform phase(gas or slurry) polymerization process.
  • the olefin polymerization catalyst of the present invention is prepared by first mixing an organic compound of Formula 1; an organometallic compound of Formula 2 and an aluminoxane, and then adding thereto a reaction mixture of an organic transition metal compound of Formula 3 and an aluminoxane, and mixing, wherein: [Formula 1] R 1 -H or R 1 -Q-R 1
  • R 1 is a cyclic hydrocarbyl group of 5 to 30 carbon atoms having at least 2 conjugated double bonds
  • Q is a divalent group for bridging R 1 s selected from the group consisting of (CR 5 2 ) b , (SiR 5 2 ) b , (GeR 5 2 ) b , NR 5 and PR 5
  • the substituent R 5 is independently a hydrogen atom, an alkyl radical of 1 to 20 carbon atoms, a cycloalkyl radical of 3 to 20 carbon atoms, an alkenyl radical of 1 to 20 carbon atoms, an aryl radical of 6 to 20 carbon atoms, an alkylaryl radical of 7 to 20 carbon atoms or an arylalkyl radical of 7 to 20 carbon atoms
  • b is an integer of 1 to 4, when Q is (CR 5 2 ) b , (SiR 5 2 ) b or (GeR 5 2 ) b , the two substituent
  • M 1 is an element selected from the group consisting of elements of Group 1, 2, 12, 13 and 14 of the Periodic Table
  • R 2 , R 3 , R 4 and R 6 are independently a hydrocarbyl group of 1 to 24 carbon atoms, an amide group, an alkoxy group or a halogen atom
  • m, n, p and q are independently 0 or 1
  • m+n+p+q is equal to the valence of M 1 .
  • M 2 is titanium(Ti), zirconium(Zr) or hafnium(Hf), R 7 is a cyclic hydrocarbyl group of 5 to 30 carbon atoms having at least 2 conjugated double bonds, X is a halogen atom, r is 0 or 1, s is an integer of 3 or 4, and r+s is equal to the valence of metal M 2 .
  • the organic compound of Formula 1 is explained as follows.
  • R 1 is a cyclic hydrocarbyl group of 5 to 30 carbon atoms having at least 2 conjugated double bonds.
  • the cyclic hydrocarbyl group of 5 to 30 carbon atoms having at least 2 conjugated double bonds can be substituted or non- substituted, and the number of the conjugated double bond is preferably 2 to 4, and more preferably 2 or 3.
  • the number of the carbon atoms of the cyclic hydrocarbyl group is preferably 5 to 13.
  • Examples of the cyclic hydrocarbyl group include cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, azulene, substituted azulene, fluorene, and substituted fluorene group.
  • R 1 can be partially substituted with 1 to 6 substituents.
  • the substituent can be selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 3 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, a haloalkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an arylalkyl group of 6 to 20 carbon atoms, an arylsilyl group of 6 to 20 carbon atoms, an alkylaryl group of 6 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an alkylsiloxy group of 1 to 20 carbon atoms, an aryloxy group of 6 to 20 carbon atoms, a halogen atom, an amino group and the mixtures thereof.
  • Q is a divalent group selected from the group consisting of (CR 5 2 ) b , (SiR 5 2 ) b , (GeR 5 2 ) b , NR 5 and PR 5 for bridging R 1 , wherein the substituent R 5 is independently a hydrogen atom, an alkyl radical of 1 to 20 carbon atoms, a cycloalkyl radical of 3 to 20 carbon atoms, an alkenyl radical of 1 to 20 carbon atoms, an aryl radical of 6 to 20 carbon atoms, an alkylaryl radical of 7 to 20 carbon atoms or arylalkyl radical of 7 to 20 carbon atoms, b is an integer of 1 to 4, preferably an integer of 1 or 2, when Q is (CR 5 2 ) b , (SiR 5 2 ) b or (GeR 5 2 ) b , the two substituents R 5 that are bonded to carbon(C), silicon(Si), germanium(Ge) can be connected with each
  • Examples of the organic compound of Formula 1 include cyclopentadiene, methylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, butylcyclopentadiene, isobutylcyclopentadiene, octadecylcyclopentadiene, cyclopentylcyclopentadiene, cyclohexylcyclopentadiene, 1,3-butylmethyl cyclopentadiene, indene, 1-methylindene, 2-methylindene, 1-ethylindene, 2-ethylindene, 1-propylindene, 2-propylindene, 2-phenylindene, 3-phenylindene, and fluorene, which can be used alone or as mixtures of two or more thereof.
  • organic compound of Formula 1 examples include bis(indenyl)ethane, bis(4,5,6,7-tetrahydro-1-indenyl)ethane, 1,3-propandinyl-bis(indene), 1,3-propandinyl-bis(4,5,6,7-tetrahydro-1-indene), propylene-bis (indene), diphenylmethylene-bis(indene), propylene-bis(fluorene), and ' diphenylmethylene-bis(fluorene), which can be used alone or as mixtures of two or more thereof.
  • the organometallic compound of Formula 2 is explained as follows.
  • M 1 is an element selected from the group consisting of elements of Group 1, 2, 12, 13 and 14 of the Periodic Table.
  • M 1 includes Lithium(Li), Sodium(Na), Potassium(K), Magnesium(Mg), Zinc(Zn), Boron(B), Aluminum(Al), Gallium(Ga), Indium(In), and Thallium(Tl)
  • M 1 is Lithium(Li), Sodium(Na), Magnesium (Mg) or Aluminum (Al).
  • R 2 , R 3 , R 4 and R 6 are independently a hydrocarbyl group of 1 to 24 carbon atoms, preferably, a hydrocarbyl group of 1 to 12 carbon atoms, an amide group, an alkoxy group or a halogen atom.
  • R 2 , R 3 , R 4 and R 6 can be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, and octyl, a cycloalkyl group such as cyclopentyl, cyclohexyl, and cycloheptyl, an aryl group such as phenyl, an arylalkyl group such as benzyl m, n, p and q are independently an integer of 0 or 1, and m+n+p+q is equal to the valence of M 1 .
  • alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, and octyl
  • a cycloalkyl group such as
  • organometallic compound of Formula 2 examples include lithium, sodium, potassium, magnesium, aluminum, methyl lithium, ethyl lithium, propyl lithium, butyl lithium, isobutyl lithium, lithium amide, lithium dimethylamide, benzyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, ethyl magnesium bromide, dibutyl magnesium, heptylbutyl magnesium, diheptyl magnesium, triethyl aluminum, trimethyl aluminum, triisobutyl aluminum, thallium ethoxide diethyl zinc, and dimethyl zinc, which can be used alone or as mixtures of two or more thereof.
  • the organic transition metal compound of Formula 3 is explained as follows.
  • M 2 is titanium(Ti), zirconium(Zr) or hafnium(Hf), R 7 is a non-substituted or substituted cyclic hydrocarbyl group of 5 to 30 carbon atoms having at least 2 conjugated double bonds.
  • the number of the conjugated double bond is preferably 2 to 4, and more preferably 2 or 3, and the number of the carbon atoms of the cyclic hydrocarbyl group is preferably 5 to 13.
  • R 7 examples include a cyclopentadienyl, a substituted cyclopentadienyl, an indenyl, a substituted indenyl, an azulenyl, a substituted azulenyl, a fluorenyl, and a substituted fluorenyl group.
  • R 7 can be partially substituted with 1 to 6 substituents.
  • the substituent can be selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, a haloalkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an arylalkyl group of 6 to 20 carbon atoms, an arylsilyl group of 6 to 20 carbon atoms, an alkylaryl group of 6 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an alkylsiloxy group of 1 to 20 carbon atoms, an aryloxy group of 6 to 20 carbon atoms, a halogen atom, an amino group and the mixtures thereof.
  • R 7 can be the same hydrocarbyl group defined for R 1 of Formula 1.
  • X is a halogen atom
  • r is an integer of 0 or 1
  • s is an integer of 3 or 4
  • r+s is equal to the valence of metal M 2 .
  • Examples of the organic transition metal compound of Formula 3 include titanium fluoride, titanium chloride, titanium bromide, titanium iodide, zirconium fluoride, zirconium chloride, zirconium bromide, zirconium iodide, hafnium fluoride, hafnium chloride, hafnium bromide, hafnium iodide, cyclopentadienyl titanium trifluoride, cyclopentadienyl titanium trichloride, cyclopentadienyl titanium tribromide, cyclopentadienyl titanium triiodide, cyclopentadienyl zirconium trifluoride, cyclopentadienyl zirconium trichloride, cyclopentadienyl zirconium tribromide, cyclopentadienyl zirconium triiodide, cyclopentadienyl hafnium trifluoride, cycl
  • the aluminoxane is used as an activator and for scavenging impurities, and can be represented by the following Formula 4.
  • R' is a hydrocarbyl radical of 1 to 10 carbon atoms, and x is an integer of 1 to 70.
  • the aluminoxane may have a linear, a cyclic, or a network structure, and the linear aluminoxane can be represented by the following Formula 5 and the cyclic aluminoxane can be represented by the following Formula 6.
  • R' is a hydrocarbyl radical, and preferably a linear or a branched alkyl radical of 1 to 10 carbon atoms. More preferably, most of R' is methyl groups.
  • x is an integer of 1 to 50, and preferably an integer of 10 to 40.
  • y is an integer of 3 to 50, and preferably an integer of 10 to 40.
  • the alkyl aluminoxane is commercially available, and the examples of alkyl aluminoxane include methylaluminoxane, ethylaluminoxane, butylaluminoxane, isobutylaluminoxane, hexylaluminoxane, and octylaluminoxane, decylaluminoxane.
  • the aluminoxane is commercially available in various forms of hydrocarbon solutions.
  • Preferable aluminoxane is an aromatic hydrocarbon solution of aluminoxane, and more preferable aluminoxane is an aluminoxane dissolved in toluene.
  • a single aluminoxane or mixtures of more than one aluminoxanes can be used.
  • the alkyl aluminoxane can be prepared by various conventional methods.
  • the alkyl aluminoxane can be prepared by adding proper amount of water to trialkylaluminum, or, by reacting a hydrocarbyl compound having water or an inorganic hydrated salt with trialkylaluminum.
  • a mixture of linear aluminoxane and cyclic aluminoxane is obtained.
  • the olefin polymerization catalyst according to the present invention can be prepared by mixing 0.2 to 20 mole, preferably 0.5 to 10 mole of the organic compound of Formula 1, 0.22 to 22 mole, preferably 0.55 to 11 mole of the organometallic compound of Formula 2, and 1 to 100,000 mole, preferably 5 to 2,500 mole of aluminum of the aluminoxane with respect to 1 mole of the organic transition metal compound of Formula 3.
  • the four compounds can be mixed for 5 minutes to 24 hours, preferably 15 minutes to 16 hours simultaneously.
  • the organic compound of Formula 1, the organometallic compound of Formula 2 and the aluminoxane are first mixed for 5 minutes to 10 hours, preferably for 15 minutes to 4 hours, and then, a reaction mixture of the organic transition metal compound of Formula 3 and the aluminoxane is added thereto and mixed for 5 minutes to 24 hours, preferably for 15 minutes to 16 hours.
  • the 4 compounds can be mixed by various ways, and conventionally, mixed under an inert atmosphere of nitrogen or argon, without a solvent, or in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene, xylene or mixtures thereof.
  • the temperature of the mixing process is 0 to 150°C, preferably 10 to 90°C.
  • the catalyst solution in which the catalyst is uniformly dissolved in the hydrocarbon solvent can be used as it stands, or the catalyst in a solid powder state in which the solvent is removed can be used.
  • the catalyst in a solid powder state can be prepared by carrying out a precipitation reaction of the catalyst solution, and solidifying the precipitate
  • the present invention also provides an olefin polymerization catalyst in which the catalyst including the organic compound of Formula 1, the organometallic compound of Formula 2, the organic transition metal compound of Formula 3, and the aluminoxane is contacted with an organic or inorganic carrier. Therefore, the catalyst of the present invention can be supported by a carrier or may form an insoluble particle with the carrier.
  • a solution state catalyst is prepared by mixing the organic compound of Formula 1, the organometallic compound of Formula 2, the organic transition metal compound of Formula 3, and the aluminoxane, and the catalyst is contacted with a porous carrier(For example, a silica carrier having pore sizes of 50 to 500 ⁇ and a pore volume of 0.1 to 5.0 cm 3 /g) to form a slurry.
  • a porous carrier for example, a silica carrier having pore sizes of 50 to 500 ⁇ and a pore volume of 0.1 to 5.0 cm 3 /g
  • the catalyst of the slurry state is treated with an acoustic wave or oscillating wave having the frequency of 1 to 10,000kHz at 0°C to 120°C for 1 to 6 hours to uniformly infiltrate the catalyst components into the pores of the carrier.
  • the catalyst slurry is dried under vacuum or nitrogen flow to form a catalyst of a solid powder state.
  • the acoustic wave or oscillating wave is preferably ultrasonic waves, and more preferably has the frequency of 20 to 500 kHz.
  • the contacting process of the catalyst and the carrier may further include the step of washing the supported catalyst with a hydrocarbon selected from the group consisting of pentane, hexane, heptane, isoparaffin, toluene, xylene and mixtures thereof.
  • the carrier can be a material having micro pores and a large surface area, and includes an inorganic carrier such as a porous inorganic compound, and inorganic salt, and an organic carrier such as an organic compound.
  • the inorganic carrier may be in any shape such as powder, particle, flake, foil and fiber under the condition that the shape can be maintained while supporting the catalyst. Regardless of the shape of the inorganic carrier, the maximum length of the inorganic carrier is generally from 5 to 200 ⁇ m, preferably from 10 to 100 ⁇ m, the preferable surface area of the inorganic carrier is 50 to 1,000 m 2 /g and the preferable pore volume is 0.05 to 5 cm 3 /g.
  • the inorganic carrier is treated to remove water or hydroxyl group thereform before use. The treatment can be carried out by calcining the carrier at 200°C to 900°C under an inert atmosphere such as air, nitrogen, or argon.
  • Examples of the inorganic salt or the inorganic carrier include silica, alumina, bauxite, zeolite, MgCl 2 , CaCl 2 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 , and mixtures thereof, such as SiO 2 -MgO, SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -V 2 O 5 , SiO 2 -CrO 3 , or SiO 2 -TiO 2 -MgO. Small amount of carbonate, sulfate, or nitrate can be added to these compounds.
  • organic carrier examples include starch, cyclodextrin, or synthetic polymer.
  • Examples of the solvent, which is used for contacting the catalyst of the present invention into the carrier include an aliphatic hydrocarbon solvent, such as pentane, hexane, heptane, octane, nonane, decane, undecane, or dodecane; an aromatic hydrocarbon solvent, such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, or toluene; and a halogenated aliphatic hydrocarbon solvent, such as dichloromethane, trichloromethane, dichloroethane, or trichloroethane.
  • the solvent or the mixtures thereof can be used for the supporting process.
  • the olefin polymerization catalyst of the present invention which contacts with the carrier preferably includes 0.2 to 20 mole, preferably 0.5 to 10 mole of the organic compound of Formula 1, and 1 to 1,000 mole, preferably 1 to 500 mole of aluminum of the aluminoxane with respect to 1 mole of the organic transition metal compound of Formula 3.
  • the olefin polymerization catalyst of the present invention includes not only a catalyst of a uniform solution state, but also a catalyst supported with an inorganic carrier(silica, alumina, and silica-alumina mixture) or an insoluble particle of the catalyst and the carrier.
  • the present invention also provides an olefin polymerization method including the step of polymerizing at least one olefin in the presence of the polymerization catalyst of the present invention.
  • the catalyst of the present invention includes not only a catalyst of a uniform solution state, but also a catalyst supported with an inorganic carrier(silica, alumina, and silica-alumina mixture) or an insoluble particle of the catalyst and the carrier.
  • the olefin polymerization method of the present invention can be carried out by a solution phase, a slurry phase, a bulk phase or a gas phase polymerization reaction.
  • the conditions for the polymerization reactions can be varied according to the state of the catalyst(homogeneous or heterogeneous phase(supported phase)), the polymerization method (solution polymerization, slurry polymerization, gas phase polymerization), target polymer properties or the polymer shape. Such variation can be easily carried out by a skilled person in the art.
  • a solvent or olefin may work as a reaction medium.
  • One or two or more olefins can be used for the polymerization.
  • Exemplary solvent includes propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, 1,2-dichloroethane, or chlorobenzene, and, if desired, mixtures of the solvents can be used.
  • the olefin polymerization catalyst of the present invention can be used for a copolymerization of a monomer/a comonomer as well as a polymerization of a monomer.
  • Preferable examples of the olefin for the polymerization or the copolymerization include ⁇ -olefins, cyclic olefins, dienes, trienes, and styrenes.
  • the ⁇ -olefin includes an aliphatic olefin of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more specifically includes ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4-methylpentene-1, 3-methylpentene-1, heptene-1, octene-1, decene-1, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, or 3,4-dimethyl-1-hexene.
  • the ⁇ -olefin may be polymerized to form a single polymer, an alternating copolymer, a random copolymer or a block copolymer.
  • the copolymerization of the ⁇ -olefin includes the copolymerization of ethylene and ⁇ -olefin of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms(ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1) and the copolymerization of propylene and ⁇ -olefin of 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms(propylene and butene-1, propylene and 4-methylpentene-1, propylene and 4-methylbutene-1, propylene and hexene-1, propylene and octene-1).
  • the amount of the other ⁇ -olefin may be less than 90 mole% with respect to the total monomer.
  • the amount of the other ⁇ -olefin may be less than 40 mole%, preferably less than 30 mole%, and more preferably less than 20 mole% with respect to the total monomer.
  • the amount of the other ⁇ -olefin may be 1 to 90 mole%, preferably 5 to 90 mole%, and more preferably 10 to 70 mole% with respect to the total monomer.
  • the carbon number of the cyclic olefin is 3 to 24, preferably 3 to 18.
  • cyclic olefin examples include cyclopentene, cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbonene, 5-methyl-2-norbonene, 5-ethyl-2-norbonene, 5-isobutyl-2-norbonene, 5,6-dimethyl-2-norbonene, 5,5,6-trimethyl-2-norbonene, and ethylene norbonene.
  • the cyclic olefin can be copolymerized with the ⁇ -olefin, and the amount of the cyclic olefin is 1 to 50 mole%, preferably 2 to 50 mole% with respect to the copolymer.
  • the preferable dienes and trienes include a polyene of 4 to 26 carbon atoms having two or three double bonds.
  • Specific examples of the dienes and the trienes include 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, and 2-methyl-1,3-butadiene.
  • Preferable examples of the styrenes include styrene or substituted styrene substituted with an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, a halogen group, an amine group, a silyl group, and a halogenated alkyl group.
  • the amount of the organic transition metal compound of Formula 3 can be varied in wide range.
  • the central metal concentration of the organic transition metal compound of Formula 3 is preferably 10 -8 to 10 1 mol/l, and more preferably 10 -7 to 10 -2 mol/l in a polymerization reaction system
  • the polymerization temperature can also be varied in wide range according to reactants, and reaction conditions.
  • the temperature is generally 0 to 250°C, and more preferably 10 to 200°C.
  • the temperature is generally 0 to 120°C, and more preferably 20 to 100°C.
  • the polymerization pressure is generally atmospheric pressure to 500kg/cm 2 , and more preferably atmospheric pressure to 50kg/cm 2 .
  • the polymerization reaction can be carried out in a batch type, a semi-continuous type, or a continuous type reaction. In addition, the polymerization can be carried out by two or more steps of different reaction conditions.
  • the molecular weight of the polymer produced with the olefin polymerization catalyst of the present invention can be controlled by changing the polymerization temperature, or by injecting hydrogen into a reactor.
  • the olefin polymerization catalyst of the present invention can be used for a prepolymerization of olefin monomer(s) for polymerization of a monomer or for copolymerization of a monomer/a comonomer.
  • the olefin polymer or copolymer is produced in the amount of 0.05 to 500g, preferably 0.1 to 300g, and more preferably 0.2 to 100g with respect to 1g of the catalyst.
  • Examples of the olefin, which is suitable for the prepolymerization include ⁇ -olefin of 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 3-methyl-1-butene, and 3-methyl-1-pentene. More suitable olefin for the prepolymerization is the same olefin which is used in a main polymerization.
  • the olefin polymerization catalyst was produced with Schlenk method in which air and moisture were completely blocked, and purified and dried nitrogen was used as an inert gas. Solvent was dried with sodium metal under inert nitrogen atmosphere. Melt Index(MI) and HLMI(high load Melt Index) of polymer were measured in accordance with ASTM D1238, and a density of polymer was measured in accordance with ASTM D1505.
  • a stainless autoclave reactor of 1L having a jacket for supplying cooling water for controlling a polymerization temperature was purged with isobutane(one time) and ethylene(five times) at 85°C to remove impurities, and then cooled to room temperature.
  • Dried hexane 300ml and triisobutylaluminum(TIBAL, impurity scavenger) 0.5mmol were added into the reactor at room temperature, and heated to a polymerization temperature of 70°C.
  • the obtained catalyst solution was directly added into the reactor, and then the reaction pressure was increased to 14 psig with ethylene(pressure 10psig). The polymerization was carried out for 1 hour, and then reaction gas was discharged, and the reactor was cooled to complete the polymerization reaction.
  • a solution including 300mL of methanol and 5% of HCI was added to the reactant and stirred for about 2 hours to neutralize the MAO component and the active catalyst component remained in the reactant.
  • a slurry including the obtained polymer was filtered and washed with water of 2 liters to remove HCl component, and the washed polymer was dried at 60 °C to produce 45g of polymer.
  • the catalytic activity of polymerization was 5350 g polymer/ mol Zr ⁇ hour, and MI((Melt Index) of the obtained polymer was 0.08g/10min, and the density of the obtained polymer was 0.9419 g/cm 3 .
  • a stainless autoclave reactor of 2L having a jacket for supplying cooling water for controlling a polymerization temperature was purged with isobutane(1 time) and ethylene(5 times) at 110°C to remove impurities, and then cooled to 80°C.
  • Isobutane 900ml and triisobutylaluminum(impurity scavenger) 1.0 mmol were added into the washed reactor, and stirred at 80°C.
  • Isobutane 100ml and the obtained supported catalyst 98mg were added into the reactor, and then ethylene and 35ml of 1-hexene were added until the partial pressure of ethylene became 110 psig.
  • the polymerization was carried out at 80°C for 90 minutes while maintaining the total pressure of the reactor to 290 psig. During the polymerization, the partial pressure of ethylene was maintained to 110 psig, and 1-hexene was continuously supplied with a speed of 0.28 ml/minute. After completion of the polymerization, unreacted 1-hexene and isobutane were discharged, and the polymer 59g having free flowability was obtained from the reactor.
  • the catalytic activity of polymerization was 410 g polymer/ g ⁇ catalyst ⁇ hour, and MI((Melt Index) of the obtained polymer was 0.007 g/10min.
  • indene 61ml 60.85 mg; 0.524.mmol
  • normalbutyl lithium 35.5mg (0.57mmol
  • MAO methyl aluminoxane
  • silica (Sylopol 948) 5g calcined at 220°C was added to the produced catalyst solution, and ultrasonic wave was applied for 1 hour, and the supernatant was discarded. The remaining solid particles were washed with hexane(1 time), and dried in vacuum to obtain a supported catalyst which was solid powder having free flowability.
  • the polymerization was carried out for 74 minutes in accordance with the polymerization method of Example 2 to obtain the polymer 195 g.
  • the catalytic activity of polymerization was 1,587 g polymer/ g ⁇ catalyst ⁇ hour, and MI((Melt Index) of the obtained polymer was 1.89 g/10min, and the density of the obtained polymer was 0.9287 g/cm 3 .
  • the polymerization was carried out for 90 minutes in accordance with the polymerization method of Example 2 to obtain the polymer 230 g.
  • the catalytic activity of polymerization was 1,533 g polymer/ g ⁇ catalyst ⁇ hour, and MI((Melt Index) of the obtained polymer was 0.98 g/10min, and the density of the obtained polymer was 0.9278 g/cm 3 .
  • the polymerization was carried out for 90 minutes in accordance with the polymerization method of Example 2 to obtain the polymer 137 g.
  • the catalytic activity of polymerization was 836 g polymer/ g ⁇ catalyst ⁇ hour, and MI((Melt Index) of the obtained polymer was 0.43 g/10min, and the density of the obtained polymer was 0.9291 g/cm 3 .
  • indene 54 ml (53.86 mg; 0.464 mmol), normalbutyl lithium 33.3 mg (0.52 mmol) and methyl aluminoxane(MAO, Albemarle company, 10% toluene solution) 20ml were mixed and stirred for 2 hours at room temperature, and then cyclopentadienyl zirconium trichloride 55 mg (0.21 mmol) was added and stirred at 30°C for 2 hours.
  • silica 4g calcined at 220°C was added to the produced catalyst solution, and ultrasonic wave was applied for 1 hour, and the supernatant was discarded. The remaining solid particles were washed with hexane(1 time), and dried in vacuum to obtain a supported catalyst which was solid powder having free flowability.
  • the polymerization was carried out for 90 minutes in accordance with the polymerization method of Example 2 to obtain the polymer 295 g.
  • the catalytic activity of polymerization was 1,967 g polymer/ g ⁇ catalyst ⁇ hour, and MI((Melt Index) of the obtained polymer was 0.95 g/10min, and the density of the obtained polymer was 0.9239 g/cm 3 .
  • indene 55 ml (54.86 mg; 0.473 mmol) and normalbutyl lithium 34 mg (0.53 mmol) were mixed and stirred for 1 hour at room temperature, and diethylaluminum chloride 65 mg (0.54 mmol) was added thereto and stirred for 30 minutes, and methyl aluminoxane(MAO, Albemarle company, 10% toluene solution) 20ml were mixed and stirred for 10 minutes at room temperature, and then cyclopentadienyl zirconium trichloride 55 mg (0.21 mmol) was added and stirred at 60°C for 1 hour.
  • MAO methyl aluminoxane
  • silica 4g calcined at 220°C was added to the produced catalyst solution, and ultrasonic wave was applied for 1 hour, and the supernatant was discarded. The remaining solid particles were washed with hexane(1 time), and dried in vacuum to obtain a supported catalyst which was solid powder having free flowability.
  • the polymerization was carried out for 106 minutes in accordance with the polymerization method of Example 2 to obtain the polymer 375 g.
  • the catalytic activity of polymerization was 2,144 g polymer/ g ⁇ catalyst ⁇ hour, and MI((Melt Index) of the obtained polymer was 1.01 g/10min, and the density of the obtained polymer was 0.9251 g/cm 3 .
  • the polymerization was carried out for 90 minutes in accordance with the polymerization method of Example 2 to obtain the polymer 159 g.
  • the catalytic activity of polymerization was 1,060 g polymer/ g ⁇ catalyst ⁇ hour, and MI((Melt Index) of the obtained polymer was 0.004 g/10min, and the density of the obtained polymer was 0.9226 g/cm 3 .
  • the polymerization was carried out for 90 minutes in accordance with the polymerization method of Example 2 to obtain the polymer 215 g.
  • the catalytic activity of polymerization was 1,419 g polymer/ g ⁇ catalyst ⁇ hour, and MI((Melt Index) of the obtained polymer was 0.26 g/10min, and the density of the obtained polymer was 0.9144 g/cm 3 .
  • the polymerization was carried out for 90 minutes in accordance with the polymerization method of Example 2 to obtain the polymer 215 g.
  • the catalytic activity of polymerization was 1,433 g polymer/ g ⁇ catalyst ⁇ hour, and MI((Melt Index) of the obtained polymer was 0.407 g/10min, and the density of the obtained polymer was 0.9256 g/cm 3 .
  • the catalyst of the present invention has a high polymerization activity, and the produced polymer has a relatively low melt index and a relatively high molecular weight. From the melt index, the catalyst of the present invention can produce various polymers having low molecular weights. Namely, the catalyst of the present invention can be prepared by a very simple process, has a high polymerization activity, and produce various olefin polymers having relatively high molecular weights by simply changing or selecting the components thereof.
  • the polymerization catalyst of the present invention can produce various polymers having different melt indexes (MI) and molecular weights, particularly, a polymer having a relatively low melt index and a relatively high molecular weight.
  • MI melt indexes

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Claims (9)

  1. Verfahren zum Herstellen eines Olefinpolymerisationskatalysators, umfassend: zuerst Vermischen einer organischen Verbindung der Formel 1, einer metallorganischen Verbindung der Formel 2 und eines Aluminoxans und dann Zugeben dazu einer Reaktionsmischung einer organischen Übergangsmetallverbindung der Formel 3 und des Aluminoxans und Vermischen, wobei:

            [Formel 1]     R1-H oder R1-Q-R1

    in Formel 1 R1 eine cyclische Hydrocarbylgruppe von 5 bis 30 Kohlenstoffatomen mit wenigstens 2 konjugierten Doppelbindungen ist und unsubstituiert oder teilweise substituiert mit 1 bis 6 Substituenten sein kann, die ausgewählt sind aus der Gruppe, bestehend aus einer Alkylgruppe von 1 bis 20 Kohlenstoffatomen, einer Alkenylgruppe von 3 bis 20 Kohlenstoffatomen, einer Cycloalkylgruppe von 3 bis 20 Kohlenstoffatomen, einer Haloalkylgruppe von 1 bis 20 Kohlenstoffatomen, einer Arylgruppe von 6 bis 20 Kohlenstoffatomen, einer Arylalkylgruppe von 6 bis 20 Kohlenstoffatomen, einer Arylsilylgruppe von 6 bis 20 Kohlenstoffatomen, einer Alkylarylgruppe von 6 bis 20 Kohlenstoffatomen, einer Alkoxygruppe von 1 bis 20 Kohlenstoffatomen, einer Alkylsiloxylgruppe von 1 bis 20 Kohlenstoffatomen, einer Aryloxygruppe von 6 bis 20 Kohlenstoffatomen, einem Halogenatom, einer Aminogruppe und den Mischungen davon;
    Q eine divalente Gruppe ist, ausgewählt aus der Gruppe, bestehend aus (CR5 2)b, (SiR5 2)b, (GeR5 2)b, NR5 und PR5 zum Überbrücken von R1s, wobei der Substituent R5 unabhängig ein Wasserstoffatom, ein Alkylradikal von 1 bis 20 Kohlenstoffatomen, ein Cycloalkylradikal von 3 bis 20 Kohlenstoffatomen, ein Alkenylradikal von 1 bis 20 Kohlenstoffatomen, ein Arylradikal von 6 bis 20 Kohlenstoffatomen, ein Alkylarylradikal von 7 bis 20 Kohlenstoffatomen oder Arylalkylradikal von 7 bis 20 Kohlenstoffatomen ist, b eine ganze Zahl von 1 bis 4 ist, wenn Q (CR5 2)b, (SiR5 2)b oder (GeR5 2)b ist, die zwei Substituenten R5, die an Kohlenstoff (C), Silicium (Si), Germanium (Ge) gebunden sind, miteinander verbunden sein können, um einen Ring von 2 bis 7 Kohlenstoffatomen zu bilden,

            [Formel 2]     M1R2 mR3 nR4 pR6 q

    in Formel 2 M1 ein Element ist, ausgewählt aus der Gruppe, bestehend aus Elementen der Gruppe 1, 2, 12, 13 und 14 des Periodensystems, R2, R3, R4 und R6 unabhängig eine Hydrocarbylgruppe von 1 bis 24 Kohlenstoffatomen, eine Amidgruppe, eine Alkoxygruppe oder ein Halogenatom sind, m, n, p und q unabhängig 0 oder 1 sind und m+n+p+q gleich der Wertigkeit von M1 ist,

            [Formel 3]     M2R7 rXs

    in Formel 3 M2 Titan (Ti), Zirkonium (Zr) oder Hafnium (Hf) ist, R7 das gleiche ist wie für R1 definiert, X ein Halogenatom ist, r eine ganze Zahl von 0 oder 1 ist, s eine ganze Zahl von 3 oder 4 ist und r+s gleich der Wertigkeit von Metall M2 ist.
  2. Verfahren zum Herstellen eines Olefinpolymerisationskatalysators gemäß Anspruch 1, wobei der Olefinpolymerisationskatalysator mit einem organischen oder anorganischen Träger geträgert wird.
  3. Verfahren zum Herstellen eines Olefinpolymerisationskatalysators gemäß Anspruch 2, wobei der mit dem Träger geträgerte Olefinpolymerisationskatalysator hergestellt wird durch Inkontaktbringen des Olefinpolymerisationskatalysators mit einem porösen Träger, so dass ein Aufschlämmungszustand gebildet wird; Behandeln des Katalysators des Aufschlämmungszustands mit einer akustischen Welle oder oszillierenden Welle mit der Frequenz von 1 bis 10.000 kHz bei 0°C bis 120°C für 1 bis 6 Stunden, so dass die Katalysatorkomponenten gleichmäßig in die Poren des Trägers eindringen; und Trocknen der in die Poren des Trägers eingedrungenen Katalysatorkomponenten unter Vakuum oder Stickstoffstrom, so dass der Katalysator eines festen Pulverzustands gebildet wird.
  4. Verfahren zum Herstellen eines Olefinpolymerisationskatalysators gemäß Anspruch 1, wobei R1 der organischen Verbindung der Formel 1 eine cyclische Hydrocarbylgruppe von 5 bis 30 Kohlenstoffatomen mit 2 bis 4 konjugierten Doppelbindungen ist.
  5. Verfahren zum Herstellen eines Olefinpolymerisationskatalysators gemäß Anspruch 1, wobei M1 der metallorganischen Verbindung der Formel 2 Lithium (Li), Natrium (Na), Magnesium (Mg) oder Aluminium (Al) ist, R2, R3, R4 und R6 unabhängig ausgewählt sind aus der Gruppe, bestehend aus einer Hydrocarbylgruppe von 1 bis 24 Kohlenstoffatomen, einer Amidgruppe, einer Alkoxygruppe oder einem Halogenatom.
  6. Verfahren zum Herstellen eines Olefinpolymerisationskatalysators gemäß Anspruch 1, wobei R7 der organischen Übergangsmetallverbindung der Formel 3 ausgewählt ist aus der Gruppe, bestehend aus einer Cyclopentadienyl-, einer substituierten Cyclopentadienyl-, einer Indenyl-, einer substituierten Indenyl-, einer Azulenyl-, einer substituierten Azulenyl-, einer Fluorenyl-, einer substituierten Fluorenylgruppe und Mischungen davon.
  7. Verfahren zum Herstellen eines Olefinpolymerisationskatalysators gemäß Anspruch 1, wobei die Menge der organischen Verbindung der Formel 1 0,2 bis 20 mol beträgt, die Menge der metallorganischen Verbindung der Formel 2 0,22 bis 22 mol beträgt und die Menge an Aluminium des Aluminoxans 1 bis 100.000 mol, bezogen auf 1 mol der organischen Übergangsmetallverbindung der Formel 3, beträgt.
  8. Olefinpolymerisationsverfahren, umfassend einen Schritt, bei dem wenigstens ein Olefin in der Anwesenheit des durch das Verfahren gemäß einem der Ansprüche 1 bis 7 hergestellten Olefinpolymerisationskatalysators polymerisiert wird.
  9. Olefinpolymerisationskatalysator, erhältlich durch das Verfahren gemäß einem der Ansprüche 1 bis 7.
EP09800508.5A 2008-07-21 2009-06-23 Verfahren zur herstellung eines olefinpolymerisierungskatalysators und olefinpolymerisierungsverfahren damit Active EP2305719B1 (de)

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